JP4737660B2 - Herbicide composition for paddy rice with reduced phytotoxicity - Google Patents

Description

  The present invention relates to a herbicidal composition for paddy rice that is applied directly to flooded sewage paddy fields, in which phytotoxicity to paddy rice is significantly reduced.

  There are many kinds of weeds that occur in paddy fields, and their occurrence also extends over a long period from the transplanting period to the growing period of paddy rice. Therefore, it is desired to develop a herbicide that completely weeds these many weeds while not causing phytotoxicity to paddy rice. However, there are cases where conventional herbicides do not sufficiently satisfy the above-mentioned purpose, and a plurality of herbicides are added for the purpose of adding a compound having an action of reducing paddy rice phytotoxicity or expanding the herbicidal spectrum and the appropriate time range for treatment. In many cases, active compounds are mixed and used.

  Benzobicyclone (generic name) which is an active ingredient of the herbicidal composition for paddy rice of the present invention is compound name [3- (2-chloro-4-methylsulfonylbenzoyl) -4-phenylthio] bicyclo [3.2. 1] A known herbicide which is oct-3-en-2-one. This agent has a broad herbicidal spectrum against annual weeds such as Nobies and Konagi and perennial weeds such as fireflies, has high herbicidal effects on high leaf weeds, and has excellent advantages such as long residual effect . This agent is absorbed from the roots, young shoots, and foliar bases of weeds, and causes whitening symptoms to develop in the new leaves that develop after treatment, causing them to die.

  However, benzobicyclon does not affect the growth of paddy rice under normal cultivation conditions, but it can cause phytotoxicity such as growth control and stem count control in shallow paddy rice transplants and in sandy soil paddy fields. It may occur and does not always satisfy the safety against rice as well as the effectiveness against paddy weeds. In particular, the use of sandy soil fields and leaked fields, shallow planting, application of high doses due to uneven application, and abnormal conditions such as abnormally low and high temperatures immediately after herbicide application, are likely to cause phytotoxicity. Further, the benzobicyclon-containing preparation has a problem that after the preparation, when a chemical solution of a composition that has passed a certain storage period adheres to the paddy rice, it causes a stronger phytotoxicity and suppresses the growth of the paddy rice.

  An object of the present invention is to provide a herbicide composition for paddy rice containing benzobicyclon, which controls paddy field weeds and has reduced phytotoxicity to rice. In particular, it is an object of the present invention to provide a herbicide composition for paddy rice that suppresses the tendency of increasing phytotoxicity over time, which is seen in benzobicyclon-containing preparations, and reduces phytotoxicity to rice.

In order to achieve the above object, the present inventors have searched for a compound having an action of reducing phytotoxicity caused by benzobicyclone. As a result, to benzobicyclone, one or more kinds selected from calcium propionate, sodium p-toluenesulfonate, calcium acetate, ammonium acetate, sodium lactate, potassium chloride, lactic acid, succinic acid, propionic acid or urea It has been found that phytotoxicity to rice is reduced by mixing the compounds.
In addition, the present inventors also added benzobicyclone to a liquid pesticidal active ingredient at room temperature (in the present invention, a liquid pesticidal active ingredient is not only a liquid itself but also a solid or semi-solid form. It also means that when a certain agrochemical active ingredient is dissolved, suspended or emulsified in a solvent), mixing the above compounds will significantly reduce phytotoxicity and complete the present invention. did.

  That is, the present invention comprises (a) benzobicyclone and (b) calcium propionate, sodium p-toluenesulfonate, calcium acetate, ammonium acetate, sodium lactate, potassium chloride, lactic acid, succinic acid, propionic acid or urea. A herbicide composition for paddy rice with reduced phytotoxicity, comprising one or more selected compounds.

The composition of the present invention comprises:
(A) benzobicyclone, and (b) one or two selected from calcium propionate, sodium p-toluenesulfonate, calcium acetate, ammonium acetate, sodium lactate, potassium chloride, lactic acid, succinic acid, propionic acid or urea One or more compounds, preferably one or more compounds selected from calcium propionate, sodium p-toluenesulfonate, calcium acetate, ammonium acetate, potassium chloride, lactic acid, succinic acid or propionic acid, more preferably propion One or two compounds of calcium acid or sodium p-toluenesulfonate,
Is a herbicide composition for paddy rice.

  In the present invention, calcium propionate, sodium p-toluenesulfonate, calcium acetate, ammonium acetate, sodium lactate, potassium chloride, lactic acid, succinic acid, propionic acid or urea listed in (b) are generally available reagents. Or any of industrial products may be used. For example, specifically, calcium propionate reagent (same as the trade name, manufactured by Wako Pure Chemical Industries, Ltd., Nacalai Tesque), or industrial product (same as the trade name, manufactured by Ueno Pharmaceutical Co., Ltd.) , Or a reagent for sodium p-toluenesulfonate (same as the trade name, manufactured by Wako Pure Chemical Industries, Ltd., Nacalai Tesque Co., Ltd.), or sodium toluenesulfonate (trade name, Meiyu Sangyo Co., Ltd.) as an industrial product. Etc.). In addition, reagents or industrial products can be similarly used for calcium acetate, ammonium acetate, sodium lactate, potassium chloride, lactic acid, succinic acid, propionic acid or urea.

  The composition of the present invention comprises (a) 1 part by weight of benzobicyclone, (b) calcium propionate, sodium p-toluenesulfonate, calcium acetate, ammonium acetate, sodium lactate, potassium chloride, lactic acid, succinic acid Preferably, it contains 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight, of one or more compounds selected from propionic acid or urea. Further, when the composition of the present invention contains (c) an active ingredient for agricultural chemicals that is liquid at normal temperature, there is no particular limitation, but component (c) is preferably 0 with respect to 1 part by weight of component (a). 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight.

  Examples of the agrochemical active ingredient that is liquid at room temperature (c) of the present invention include pretilachlor, butachlor, MCPB-E, and the like. Although the composition of this invention may contain these 1 type, or 2 or more types, if a component (c) is a liquid agrochemical active ingredient at normal temperature, it will not be limited to these.

  In order to convert a pesticide active ingredient that is solid or semisolid at normal temperature into a pesticide active ingredient that is liquid at normal temperature of the present invention, it is preferable to dissolve in a non-volatile solvent that is liquid at normal temperature. As such a solvent, for example, a solvent having a high boiling point, a low toxicity, a high flash point, and a low viscosity is preferable, such as xylene, sorbeso, trimethylbenzene, and the like, which do not give adverse effects such as particle growth and decomposition to active ingredients of agricultural chemicals. Aromatic solvents such as benzene, methylbenzene, methylnaphthalene, alkylbenzene, phenylxylylethane; naphthenic high boiling solvents; alcohols such as hexanol, heptanol and octanol; ketones such as cyclohexanone and diacetone alcohol; ethylene glycol and diethylene glycol , Butanediol, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, ethylene glycol diethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether , Glycols such as diethylene glycol monobutyl ether acetate, diethylene glycol dibutyl ether, diethylene glycol diethyl hexyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate, tripropylene glycol methyl ether, 3-methoxy-3-methyl-1-butanol and acetate And their various esters and ethers; esters such as butyl lactate, ethyl lactate, butyl butyrate, diisotridecyl phthalate, dioctyl phthalate, methyl oleate, coconut oil fatty acid methyl ester; liquid paraffin, chlorinated paraffin , Isoparaffin, machine oil, polybutene and other paraffinic solvents; coconut oil, soybean oil, rapeseed oil and other vegetable oils; whale oil Animal oils; silicone oils and derivatives thereof; phosphoric esters such as tributyl phosphate and tristrolol phosphate; lactones such as ε-caprolactone and γ-butyllactone; alkylpyrrolidones such as N-methylpyrrolidone and N-octylpyrrolidone And various liquid surfactants. These may be used alone or in combination of two or more, but the present invention is not limited to these.

  Preferred examples of the non-volatile solvent that is liquid at room temperature used in the present invention include aromatic solvents, glycols and derivatives thereof, fatty acid esters, alkylpyrrolidones, and ketones. The usage-amount of such a solvent is 0.1-50 weight part normally in a herbicide composition, Preferably it is 1-40 weight part, More preferably, it is 2-30 weight part.

  The herbicidal composition for paddy rice of the present invention may contain, in addition to the above-mentioned components, agrochemical active ingredients such as further herbicidal active ingredients and fertilizer ingredients as necessary. The blending ratio can be appropriately designed according to the desired properties, dosage form, etc., for example, 0.01 to 60 parts by weight in the preparation, preferably 0.1 to 40 parts by weight, more preferably The range is 0.2 to 30 parts by weight. Although an agricultural chemical active ingredient is specifically illustrated below, this invention is not limited to these.

  The herbicidal composition for paddy rice of the present invention may further contain herbicidal active ingredients as listed below: for example, bensulfuron methyl, azimusulfuron, imazosulfuron, pyrazosulfuron ethyl, ethoxysulfuron, synosulfuron, cyclo Sulfamron, dimepiperate, mefenacet, molinate, pyributycarb, tenyl chlor, eprocarb, butamifos, bromobutide, diemron, caffentrol, cyhalohop butyl, benzophenap, pyrazolate, pyrazoxifene, benchocurve, cimetrin, dimetamethrin, pentoxazone, edipizalzone , Naproanilide, cinmethylin, 2,4-D and alkyl esters or salts thereof, MCPB, oxadichrome mehon Fentrazamide, indanofan, cumyluron, anilofos, bifenox, piperophos, quinoclamine, pyriminobac-methyl, clomeprop, pyraclonil, benfuresate or bentazon like.

  The herbicidal composition for paddy rice of the present invention can contain a surfactant, a dispersant, an auxiliary agent, a carrier or the like that is widely used in agricultural chemical formulations. Although the example is shown below, it is not limited to these.

  Surfactants and dispersants are not particularly limited as long as they are usually used in agrochemical formulations, for example, anionic surfactants, nonionic surfactants, and / or zwitterionic surfactants, respectively. It can be used individually or in mixture of 2 or more types. For example, nonionic surfactants such as polyoxyethylene alkyl aryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene fatty acid ester, sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid ester, alkylbenzene sulfone Acid salt, lignin sulfonate, alkyl sulfosuccinate, naphthalene sulfonate, alkyl naphthalene sulfonate, salt of formalin condensate of naphthalene sulfonic acid, salt of formalin condensate of alkyl naphthalene sulfonic acid, phenol sulfonate Condensate, polyoxyethylene alkylaryl ether sulfate and phosphate, polyoxyethylene styryl phenyl ether sulfate, phosphate and Anionic surfactants such as alkylamine salts, amino acid type or betaine type zwitterionic surfactants such as and the like. These surfactants may be used alone or in combination of two or more. Usually, 0.01 to 30 parts by weight, preferably 0.05 to 20 parts by weight, in the herbicidal composition of the present invention, More preferably, it is contained in an amount of 0.1 to 15 parts by weight.

  When the herbicidal composition for paddy rice of the present invention is an aqueous suspension preparation, for example, hydrochloric acid, phosphoric acid, sodium citrate, citric acid, disodium hydrogen phosphate are used as a buffering agent for pH adjustment. , Sodium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, phthalic acid, potassium hydrogen phthalate, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, succinic acid, sodium borate, etc. be able to. These are usually appropriately diluted with water to a concentration of about 0.1 to 5 N, and the pH of the aqueous suspension preparation is adjusted to 7.0 or less, preferably about pH 4.0 to 6.0. For the measurement of pH, an aqueous suspension preparation is measured with a stock solution using a digital pH meter (castany LAB F-13 type, manufactured by Horiba, Ltd.).

  The composition of this invention can contain a thickener further as needed. Examples of thickeners include fine powders of inorganic minerals such as smectite, sepiolite, attapulgite, laponite, montmorillonite, hectorite, cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, carboxyethylcellulose, methylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, and the like. Its salts, natural gums such as xanthan gum, welan gum, guar gum, tragacanth gum, gum arabic, various grades of dextrin, starch derivatives such as sodium carboxymethyl starch, natural products such as sodium alginate, sodium caseinate and their derivatives, Water-soluble synthetic polymers such as polyvinyl alcohol, polyacrylic acid and derivatives thereof, and polyvinylpyrrolidone Etc. Although the like, is not limited thereto, it can be used alone or in combination with several. The blending ratio of the thickener varies depending on the type of the thickener, but is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight in the herbicidal composition of the present invention, and the viscosity is It adds so that it may become 30-2000 mPa * s, Preferably it is 100-1000 mPa * s, More preferably, it is 200-600 mPa * s. The viscosity is a value measured using a digital viscometer (DVL-BII type, manufactured by Tokimec Co., Ltd.). The measurement conditions are rotor No2, rotor rotation speed 30 rpm, and formulation temperature 20 ° C.

  If necessary, other auxiliary agents can be added to the herbicidal composition for paddy rice of the present invention. For example, ethylene glycol, propylene glycol, polyethylene glycol, glycerin, etc. as an antifreezing agent are blended in an amount of 1 to 20 parts by weight, preferably 2 to 10 parts by weight, and acetylene glycol type or silicone type as an antifoaming agent. , Fluorine-based, fatty acid-based, etc. in a blending ratio of 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, and as a fungicide, benzothiazole derivatives, sorbic acid, potassium sorbate, p-oxybenzoic acid Acid butyl, glutaraldehyde, thiazolone, BNPK (2-bromo-2-nitropropane-1,3-diol) and the like are appropriately mixed at 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight. Can be added. Furthermore, as a stabilizer, an antioxidant, an ultraviolet ray inhibitor, a crystal precipitation inhibitor, and the like may be added as necessary, but the auxiliary agents are not limited to those exemplified here.

  The herbicidal composition for paddy rice of the present invention, for example, an aqueous suspension preparation or a granulated wettable powder, can be produced by various methods. For example, when wet pulverizing an agricultural chemical active ingredient, add the agricultural chemical active ingredient, surfactant, and antifoaming agent to water, mix and suspend it, and then use a wet pulverizer as shown below to obtain a predetermined particle size. Wet mill until. Next, thickener, anti-freezing agent, antibacterial agent and other auxiliary components are added to water and mixed in advance, and then dispersed and dissolved to make uniform. Further, the pH of the composition is adjusted with a pH adjuster. Thus, the herbicide composition for paddy rice of the present invention can be obtained.

  Examples of the wet pulverizer include Attritor mills such as Attritor (Mitsui Mine Co., Ltd.), Dino Mill (Shinmaru Enterprises Co., Ltd.), Sand Grinder (Imex Co., Ltd.), Apex Mill (Kotobuki Giken Co., Ltd. )), Super Apex Mill (Kotobuki Giken Kogyo Co., Ltd.), Diamond Fine Mill (Mitsubishi Heavy Industries, Ltd.), Coball Mill (Shinko Pantech Co., Ltd.), Dries Velke Pearl Mill (Nippon Eirich Co., Ltd.), etc. A hammer mill such as a bead mill, a colloid mill (Special Machine Industries Co., Ltd.), or a wet atomizer (Dalton Co., Ltd.) is used.

  The pulverization of the active ingredient is not limited to wet pulverization, and if necessary, the herbicidal active ingredient may be mixed with a mineral carrier and other auxiliary agents and pulverized to a predetermined particle size using a dry pulverizer. Is possible. The obtained pulverized product is suspended and dispersed in water together with surfactants, antifoaming agents, thickeners, antifreeze agents, antibacterial agents, and other adjuvants, mixed and homogenized, and pH adjusted. The herbicidal composition for paddy rice of the present invention can be obtained by adjusting the pH of the composition to 7.0 or less with an agent.

  Examples of dry pulverizers include jet mills such as SK-Jet O-Mizer (Seishin Company), Single Track Jet Mill (Seisin Company), ACM Pulperizer (Hosokawa Micron), Sample Mill A hammer mill such as (Dalton Co., Ltd.), a pin mill, a ball mill, a turbo mill, or the like can be used.

  Furthermore, the grinding | pulverization by these each model can be combined suitably with the grinding | pulverization of an agrochemical active ingredient. For example, after preliminarily pulverizing with a wet pulverizer such as a colloid mill or a wet atomizer, or finely pulverizing with a bead mill, or pre-wetly pulverizing the active ingredient together with a surfactant or an antifoaming agent, This can be further finely pulverized using the above-mentioned wet pulverizer. Further, after preliminary pulverization with a batch type pulverizer such as an attritor, fine pulverization with a continuous bead mill is also possible. The degree of pulverization is pulverized so that most of the active ingredients of the agricultural chemicals are 10 μm or less, preferably 0.1 to 5 μm in weight median diameter, both in wet and dry methods. The particle size of the agrochemical active ingredient is measured by a laser diffraction / light scattering particle size measuring device (LA-700, manufactured by Horiba, Ltd.).

  Hereinafter, the present invention will be described more specifically with reference to examples and test examples, but the present invention is not limited to these examples.

Example 1 Flowable (500 mL / 10a formulation)
(1) Preparation of benzobicyclon slurry 46.18 parts of benzobicyclon active ingredient, Agrisol FL-2017 (polyoxyethylene styrenated phenyl ether sulfate sodium salt: manufactured by Kao Corporation) 5.00 parts, Jeropon SM-100 (Anionic polymer: Rhône-Poulein Co., Ltd.) 2.50 parts, Antihome E-20 (Silicon 20% liquid: Kao Co., Ltd.) 0.25 parts, SMA-1440H (styrene / maleic anhydride copolymer) Material: 1.62 parts by Fujii Yoshitsusho Co., Ltd., calcium propionate (Ueno Pharmaceutical Co., Ltd.) 5.00 parts, and water 39.45 parts, 1NS attritor (steel balls 17 kg, slurry 2) And pulverized for 20 minutes with a 5 kg charge, 200 rpm: manufactured by Mitsui Mining Co., Ltd. to obtain a benzobicyclon slurry.

(2) Preparation of pretilachlor emulsion 19.20 parts of pretilachlor raw material, 11.11 parts of SOPPROHOR BSU (polyoxyethylene tristyryl phenyl ether: manufactured by Rhône-Poulenc), propylene glycol (manufactured by Mitsui Chemicals) 11. 11 parts, 0.22 part of Antihome E-20, 7.33 parts of Disrol AQ3 (Poval-modified acrylic ester copolymer: manufactured by Nippon Emulsifier Co., Ltd.), 6.36 parts of SMA-1440H and 44.67 of water The parts were mixed with a three-one motor 1200G for 30 minutes to obtain a pretilachlor emulsion.

(3) Preparation of flowable 9.28 parts of benzobicyclon slurry, 45.00 parts of pretilachlor emulsion, 10.60 parts of 5% aqueous dispersion of Kunipia F (purified bentonite: manufactured by Kunimine Industries, Ltd.), load pole 23 ( 14.00 parts of 1% aqueous solution of xanthan gum (Rhône-Poulenc), Proxel GXL (30% dipropylene glycol solution of benzothiazole derivative: Avicia) 0.10 parts, 1.75 parts of 1.2N hydrochloric acid And 17.27 parts of water were mixed with Three One Motor 1200G for 30 minutes to obtain a flowable of the present invention having a product pH of 5.0 containing 4.3% benzobicyclone and 8.6% pretilachlor.

Example 2 Flowable (500 mL / 10a formulation)
Instead of calcium propionate described in Example 1, sodium toluene sulfonate (manufactured by Meitomo Sangyo Co., Ltd.) was used, and 1.83 parts of 1.2N hydrochloric acid was used. A flowable of the present invention having a product pH of 5.0, containing 4.3% of benzobicyclone and 8.6% of pretilachlor was obtained.

Example 3 Flowable (500 mL / 10a formulation)
Instead of the calcium propionate described in Example 1, calcium acetate (reagent: manufactured by Nacalai Tesque) was used, except that 3.35 parts of 1.2N hydrochloric acid was used. A flowable of the present invention having a product pH of 5.0 containing benzobicyclone 4.3% and pretilachlor 8.6% was obtained.

Example 4 Flowable (500 mL / 10a formulation)
Instead of the calcium propionate described in Example 1, ammonium acetate (reagent: manufactured by Nacalai Tesque Co., Ltd.) was used, except that 1.84 parts of 1.2N hydrochloric acid was used. A flowable of the present invention having a product pH of 5.8, containing 4.3% benzobicyclone and 8.6% pretilachlor was obtained.

Example 5 Flowable (500 mL / 10a formulation)
Instead of the calcium propionate described in Example 1, sodium lactate (reagent: manufactured by Nacalai Tesque) was used, except that 1.84 parts of 1.2N hydrochloric acid was used. A flowable of the present invention having a product pH of 5.4 containing 4.3% benzobicyclone and 8.6% pretilachlor was obtained.

Example 6 Flowable (500 mL / 10a formulation)
Instead of the calcium propionate described in Example 1, potassium chloride (reagent: manufactured by Nacalai Tesque) was used, and except that 1.84 parts of 1.2N hydrochloric acid was used, exactly the same as Example 1, A flowable of the present invention with a product pH of 5.2 containing 4.3% benzobicyclone and 8.6% pretilachlor was obtained.

Example 7 Flowable (500 mL / 10a formulation)
In place of calcium propionate described in Example 1, lactic acid (reagent: manufactured by Nacalai Tesque) was used, and 4% sodium hydroxide (reagent: manufactured by Nacalai Tesque) was used and adjusted to 4% with purified water. ) Except for using 1.30 parts, the flowable of the present invention having a product pH of 5.0 containing 4.3% benzobicyclone and 8.6% pretilachlor was obtained in the same manner as in Example 1.

Example 8 Flowable (500 mL / 10a formulation)
Instead of calcium propionate described in Example 1, succinic acid (reagent: manufactured by Nacalai Tesque) was used, and except that 1.84 parts of 1.2N hydrochloric acid was used, exactly the same as Example 1, A flowable of the present invention having a product pH of 4.0 containing 4.3% benzobicyclone and 8.6% pretilachlor was obtained.

Example 9 Flowable (500 mL / 10a formulation)
Instead of calcium propionate described in Example 1, propionic acid (reagent: manufactured by Nacalai Tesque Co., Ltd.) was used and 1.04 parts of 4% sodium hydroxide was used. A flowable of the present invention having a product pH of 5.0, containing 4.3% of benzobicyclone and 8.6% of pretilachlor was obtained.

Example 10 Flowable (500 mL / 10a formulation)
In the same manner as in Example 1, except that urea (reagent: manufactured by Nacalai Tesque) was used instead of calcium propionate described in Example 1, and 1.82 parts of 1.2N hydrochloric acid was used, A flowable of the present invention having a product pH of 5.0 containing bicyclon 4.3% and pretilachlor 8.6% was obtained.

Example 11 Granule wettable powder (125 g / 10a formulation)
After mixing 4.42 parts of Bensulfuron methyl base, 23.50 parts of Caventrol main body, 42.26 parts of Daimlon base and 16.80 parts of benzobicyclon base, air mill (JOM-0101 type, supply amount: 3. 7 kg / H: crushed once by Seishin Enterprise Co., Ltd. Powder premix obtained with a kneader (FM-NW-5 type: manufactured by Fuji Sangyo Co., Ltd.), 0.40 part of toluenesulfonic acid sodium, New Coal 291PG (70% alkylsulfosuccinate solution: Japanese emulsifier ( 0.40 part, M-3801G (α-olefin sulfonate: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), KS-538 (silicon: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.80 Part, Sun extract P252 (lignin sulfonate: Nippon Paper Industries Co., Ltd.) 7.42 parts and kneading water was added and kneaded, then dome gran (DG-L1 type, screen 0.5 mmφ: Dalton Co., Ltd.) Made by extrusion) and dried using a dryer (blow shelf type dryer, blown temperature of 90 ° C. for 2 hours: manufactured by Tabai Co., Ltd.). The obtained dried grains were sized using a JIS sieve having an opening diameter of 350 μm and 850 μm, and Bensulfuron methyl 4.4%, Cavenstrol 23.1%, Daimlon 42.0%, and benzobicyclone 16.80%. A granular wettable powder was obtained.
375 g of water is mixed with 125 g of the obtained granulated wettable powder, mixed and dispersed, and contains bensulfuron methyl 1.1%, caffentrol 5.8%, diemron 10.5%, benzobicyclone 4.2%. An aqueous suspension of the invention with a product pH of 6.5 was obtained.

Comparative Example 1 Flowable (500 mL / 10a formulation)
A flowable product having a pH of 5.0, containing 4.3% benzobicyclone and 8.6% pretilachlor, exactly as in Example 1 except that calcium propionate was omitted from the flowable of Example 1. Obtained.

Comparative Example 2 Flowable (500 mL / 10a formulation)
Product pH 7 containing benzobicyclon 4.3% and pretilachlor 8.6% exactly as in Example 1 except that calcium propionate and 1.2N hydrochloric acid were omitted from the flowable of Example 1. Obtained 2 flowables.

Comparative Example 3 Flowable (500 mL / 10a formulation)
A flowable product having a pH of 5.0 and containing 4.3% benzobicyclone and 8.6% pretilachlor in exactly the same manner as in Example 2 except that sodium toluenesulfonate was omitted from the flowable of Example 2. Got.

Comparative Example 4 Flowable (500 mL / 10a formulation)
A flowable product pH 4.7 containing benzobicyclone 4.3% and pretilachlor 8.6% was obtained in the same manner as in Example 3 except that calcium acetate was omitted from the flowable of Example 3. It was.

Comparative Example 5 Flowable (500 mL / 10a formulation)
Except that ammonium acetate was omitted from the flowable of Example 4, a flowable of product pH 5.2 containing 4.3% benzobicyclon and 8.6% pretilachlor was obtained in the same manner as Example 4. It was.

Comparative Example 6 Flowable (500 mL / 10a formulation)
A flowable product of pH 5.4 containing 4.3% benzobicyclone and 8.6% pretilachlor was obtained in the same manner as in Example 5 except that sodium lactate was omitted from the flowable of Example 5. It was.

Comparative Example 7 Flowable (500 mL / 10a formulation)
In the flowable of Example 6, except that potassium chloride was omitted, a flowable product of pH 5.0 containing benzobicyclone 4.3% and pretilachlor 8.6% was obtained in the same manner as Example 6. It was.

Comparative Example 8 Flowable (500 mL / 10a formulation)
Of the flowable of Example 7, except that lactic acid was omitted, a flowable of product pH 5.3 containing benzobicyclone 4.3% and pretilachlor 8.6% was obtained in the same manner as Example 7. .

Comparative Example 9 Flowable (500 mL / 10a formulation)
In the flowable of Example 8, except that succinic acid was omitted, the flowable of product pH 4.0 containing benzobicyclone 4.3% and pretilachlor 8.6% was obtained in the same manner as Example 8. It was.

Comparative Example 10 Flowable (500 mL / 10a formulation)
Of the flowable of Example 9, except that propionic acid was omitted, a flowable of product pH 5.2 containing 4.3% benzobicyclon and 8.6% pretilachlor was obtained in the same manner as Example 9. It was.

Comparative Example 11 Flowable (500 mL / 10a formulation)
The flowable product pH 4.9 containing 4.3% benzobicyclone and 8.6% pretilachlor was obtained in exactly the same manner as in Example 10 except that urea was omitted from the flowable of Example 10. .

Comparative Example 12 Granule wettable powder (125 g / 10a formulation)
Except for removing sodium toluene sulfonate from the granular wettable powder of Example 11, 4.4% Bensulfuron methyl, 23.1% Caventrol, 42.0% Daimlon, A granular wettable powder containing 16.80% benzobicyclone was obtained.
375 g of water is mixed with 125 g of the obtained granulated wettable powder, mixed and dispersed, and contains bensulfuron methyl 1.1%, caffentrol 5.8%, diemron 10.5%, benzobicyclone 4.2%. An aqueous suspension with product pH 6.0 was obtained.

Test Example Test Example 1 Adherent phytotoxicity test of time-lapsed products The preparations obtained in Examples 1 to 11 and Comparative Examples 1 to 12 were placed in plastic bottles, sealed, and stored for 2 weeks in a constant temperature chamber at 50 ° C. did. The preparation before and after aging was applied according to the following procedure.
A 100 cm ² pot was filled with paddy field soil, and two 1.5-1.8 leaf stage paddy rice plants were transplanted as one strain, and the water depth was about 3 cm. 4 to 5 days after rice transplantation, 3 μL × 4 drops of the stock solution are treated with a micropipette against the center of the second leaf blade. After about 2 weeks in the greenhouse (water temperature about 25-30 ° C.), the condition of the rice was visually evaluated. The results are shown in Table 1.
(Evaluation)-: No phytotoxicity
±: Slight phytotoxicity, but no practical problem
+: There is chemical damage
++: Strong phytotoxicity
+++: Remarkably strong phytotoxicity

Test Example 2 Herbicidal Effect Test Padded paddy soil was filled in a 900 cm ² pot, and various seedlings of millet, koigi, broadleaf, and firefly were sown on the soil surface layer, and tubers of urikawa and mizugayatsuri were placed on the floor. 1.5-1.8 leaf stage paddy rice was transplanted, and the flooding depth was about 3 cm. Two days after paddy rice transplantation, the stock solution obtained in Examples 1 to 11 is uniformly treated with a micropipette by 45 μL (equivalent to a dose of 500 mL / 10a). The plants were grown in a greenhouse (water temperature of about 25 to 30 ° C.), and the herbicidal effect was evaluated after 4 weeks. The results are shown in Table 2.
(Evaluation) 10: Maximum effect ~ 0: No effect

  The herbicidal composition for paddy rice containing the benzobicyclon of the present invention is a herbicide that controls paddy weeds and has extremely little phytotoxicity to rice when applied to flooded paddy fields. According to the present invention, it is possible to suppress the phytotoxicity-increasing tendency with time, particularly seen in benzobicyclone-containing preparations, and to reduce the phytotoxicity to rice.

Claims (9)

(A) benzobicyclon, and (b) calcium propionate, sodium p- toluenesulfonic acid, calcium acetate, ammonium acetate, sodium lactate, milk acid, one or more selected or found succinic or propionic acid Compound,
A herbicidal composition for paddy rice. Furthermore, (c) active ingredients for agricultural chemicals that are liquid at room temperature,
The herbicidal composition for paddy rice according to claim 1, comprising:   (C) The herbicidal composition for paddy rice according to claim 1 or 2, wherein the active ingredient of pesticidal liquid at room temperature is one or more herbicides selected from pretilachlor, butachlor, or MCPB-E.   The herbicide composition for paddy rice according to any one of claims 1 to 3, wherein the compound (b) is one or two compounds selected from calcium propionate or sodium p-toluenesulfonate. (A) For 1 part by weight of benzobicyclone,
(B) 0.01 to 10 parts by weight of one or two compounds selected from calcium propionate or sodium p-toluenesulfonate;
(C) The herbicide composition for paddy rice according to claim 4, comprising 0.1 to 20 parts by weight of an agrochemical active ingredient which is liquid at normal temperature.   The herbicidal composition for paddy rice according to any one of claims 1 to 5, which is an aqueous suspension preparation or a granular wettable powder.   The herbicidal composition for paddy rice according to claim 6, wherein the granular wettable powder is suspended in water to obtain an aqueous suspension preparation.   The herbicidal composition for paddy rice according to claim 6 or 7, wherein the pH of the aqueous suspension preparation is 7.0 or less.   The method for applying a herbicidal composition for paddy rice according to any one of claims 1 to 8, wherein the herbicidal composition for paddy rice is applied directly to a flooded paddy field.